The combination of carbon materials and magnetic elements is considered as an effective strategy to obtain high-performance electromagnetic wave (EMW) absorption materials. However, using nanoscale regulation to the optimization of composite material dielectric properties and enhanced magnetic loss properties is facing significant challenges. Here, the dielectric constant and magnetic loss capability of the carbon skeleton loaded with Cr compound particles are further tuned to enhance the EMW absorption performance. After 700 °C thermal resuscitation of the Cr3-polyvinyl pyrrolidone composite material, the chromium compound is represented as a needle-shaped structure of nanoparticles, which is fixed on the carbon skeleton derived from the polymer. The size-optimized CrN@PC composites are obtained after the substitution of more electronegative nitrogen elements using an anion-exchange strategy. The minimum reflection loss value of the composite is -105.9 dB at a CrN particle size of 5 nm, and the effective absorption bandwidth is 7.68 GHz (complete Ku-band coverage) at 3.0 mm. This work overcomes the limitations of impedance matching imbalance and magnetic loss deficiency in carbon-based materials through size tuning, and opens a new way to obtain carbon-based composites with ultra-high attenuation capability.